US20230402651A1 - Novel compound, and additive, electrolyte and lithium secondary battery which comprise same - Google Patents

Novel compound, and additive, electrolyte and lithium secondary battery which comprise same Download PDF

Info

Publication number
US20230402651A1
US20230402651A1 US18/013,841 US202218013841A US2023402651A1 US 20230402651 A1 US20230402651 A1 US 20230402651A1 US 202218013841 A US202218013841 A US 202218013841A US 2023402651 A1 US2023402651 A1 US 2023402651A1
Authority
US
United States
Prior art keywords
group
unsubstituted
substituted
compound
electrolyte
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
US18/013,841
Other languages
English (en)
Inventor
Sangwoo Park
Hyejin Park
Seungyeop OH
Myungheui Woo
Wonseok Cho
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Samsung SDI Co Ltd
Original Assignee
Samsung SDI Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Samsung SDI Co Ltd filed Critical Samsung SDI Co Ltd
Publication of US20230402651A1 publication Critical patent/US20230402651A1/en
Pending legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes

Definitions

  • the present disclosure relates to a novel compound, an electrolyte, and a lithium secondary battery including the same.
  • Lithium secondary batteries are used as power supplies for portable electronic devices such as video cameras, mobile phones, and laptop computers.
  • Rechargeable lithium secondary batteries have a high energy density per unit weight and may be charged at a high speed as compared to existing lead storage batteries, nickel-cadmium batteries, nickel-hydride batteries, nickel-zinc batteries, etc.
  • An organic electrolyte is generally used as an electrolyte for a lithium secondary battery.
  • the organic electrolyte is prepared by dissolving a lithium salt in an organic solvent. It is preferable that an organic solvent is stable at a high voltage, has high ionic conductivity and high permittivity, and has low viscosity.
  • An aspect is to provide a novel compound capable of improving resistance characteristics during high-temperature storage, and low-temperature discharge capacity of a lithium secondary battery.
  • Another aspect is to provide an additive for a lithium secondary battery including the compound.
  • Still another aspect is to provide an electrolyte for a lithium secondary battery including the compound.
  • Still another aspect is to provide a lithium secondary battery including the compound.
  • a compound including: a cyclic sulfonyl group; and a silyl group linked thereto, the silyl group containing an unsaturated hydrocarbon group.
  • the compound may be represented by Formula 1 below:
  • an additive for a lithium secondary battery including the compound.
  • an electrolyte for a lithium secondary battery including: a lithium salt; an organic solvent; and an additive, wherein the additive includes the compound.
  • a lithium secondary battery including: a positive electrode including a positive active material; a negative electrode including a negative active material; and an electrolyte arranged between the positive electrode and the negative electrode, wherein at least one of the positive electrode, the negative electrode, and the electrolyte includes the compound.
  • a compound according to an embodiment may be used as an additive for a lithium secondary battery, and when the compound is used in an electrolyte for a lithium secondary battery as an additive, resistance characteristics during high-temperature storage, and low-temperature discharge capacity of a lithium secondary battery may be improved.
  • FIG. 1 shows a schematic diagram of a lithium secondary battery according to an embodiment.
  • FIG. 2 shows results of evaluating alternating current internal resistance (AC-IR) of coin cells according to Examples 1 to 3 and Comparative Example 1, when the coin cells are stored at a high temperature.
  • AC-IR alternating current internal resistance
  • FIG. 3 shows results of measuring internal resistance of coin cells according to Examples 1 to 3 and Comparative Example 1, by using electrochemical impedance spectroscopy (EIS), before the coin cells are stored at a high temperature.
  • EIS electrochemical impedance spectroscopy
  • FIG. 4 shows results of measuring internal resistance of coin cells according to Examples 1 to 3 and Comparative Example 1, by using EIS, 4 days after the coin cells are stored at a high temperature.
  • FIG. 5 shows results of measuring internal resistance of coin cells according to Examples 1 to 3 and Comparative Example 1, by using EIS, 10 days after the coin cells are stored at a high temperature.
  • FIG. 6 is a result of evaluating low-temperature ( ⁇ 10° C.) discharge characteristics of coin cells according to Examples 2 and 3 and Comparative Example 1.
  • a novel compound according to an embodiment includes: a cyclic sulfonyl group; and a silyl group linked thereto, the silyl group containing an unsaturated hydrocarbon group.
  • the cyclic sulfonyl group may suppress a resistance increase rate of a lithium secondary battery during high-temperature storage, and the silyl group containing an unsaturated hydrocarbon group may improve low-temperature discharge characteristics by inducing discharge of a lot of electrons when the lithium secondary battery is discharged at a low temperature.
  • a structure of a cyclic sulfonyl group has higher polarity than a linear sulfone structure, and therefore, excellent solubility may be secured without issues of precipitation in an electrolytic solution, and the cyclic sulfonyl group exhibits an effect of improving high temperature performance by being effectively adsorbed on a surface of an electrode plate.
  • the silyl group in the compound may include at least one unsaturated hydrocarbon group, and reduction polymerization of the unsaturated hydrocarbon group proceeds at an interface of an active material, compared to when there is no unsaturated hydrocarbon group, and therefore, low-temperature lithium ion conductivity may be improved by an effective protective film containing the silyl group.
  • the compound may simultaneously improve resistance during high-temperature storage, and improve low-temperature discharge capacity, in a lithium ion battery.
  • the compound may be represented by Formula 1 below:
  • R 1 to R 7 may be each independently selected from hydrogen, deuterium, a fluoro group (—F), a chloro group (—Cl), a bromo group (—Br), an iodo group (—I), a hydroxyl group, a cyano group, a nitro group, an amino group, an amidino group, a hydrazine group, a hydrazone group, carboxylic acid or a salt thereof, sulfonic acid or a salt thereof, phosphoric acid or a salt thereof, a substituted or unsubstituted C 1 -C 10 alkyl group, a substituted or unsubstituted C 2 -C 10 alkenyl group, a substituted or unsubstituted C 2 -C 10 alkynyl group, or a substituted or unsubstituted C 1 -C 10 alkoxy group; R 8 and R 9 may be each independently selected from a substituted or un
  • R 1 to R 7 may be each independently selected from hydrogen, an unsubstituted C 1 -C 8 alkyl group, an unsubstituted C 2 -C 8 alkenyl group, an unsubstituted C 2 -C 8 alkynyl group, or an unsubstituted C 1 -C 8 alkoxy group;
  • R 8 to R 9 may be each independently selected from an unsubstituted C 1 -C 8 alkyl group, an unsubstituted C 2 -C 8 alkenyl group, an unsubstituted C 2 -C 8 alkynyl group, or an unsubstituted C 1 -C 8 alkoxy group;
  • L may be selected from O, S, a carbonyl group, an unsubstituted C 1 -C 4 alkylene group, an unsubstituted C 2 -C 4 alkenylene group, an unsubstituted C 2 -C 4 alkynylene
  • the compound may be represented by Formula 2 below:
  • R 1 to R 9 in Formula 1 may be each independently selected from hydrogen, a methyl group, an ethyl group, a propyl group, an iso-propyl group, a butyl group, an iso-butyl group, a sec-butyl group, a tert-butyl group, —F, —Cl, —Br, —I, a methoxy group, an ethoxy group, an ethenyl group, an isocyanate (—N ⁇ C ⁇ O) group, and —CF 3 group.
  • R 1 to R 7 in Formula 1 may be each independently selected from hydrogen, a methyl group, an ethyl group, a propyl group, an iso-propyl group, a butyl group, an iso-butyl group, a sec-butyl group, a tert-butyl group, —F, —Cl, —Br, —I, a methoxy group, an ethoxy group, an ethenyl group, an isocyanate (—N ⁇ C ⁇ O) group, and —CF 3 group
  • R 8 and R 9 may be each independently selected from a methyl group, an ethyl group, a propyl group, an iso-propyl group, a butyl group, an iso-butyl group, a sec-butyl group, a tert-butyl group, and —CF 3 group.
  • L may be —O—, —S—, —C( ⁇ O)—, —CH 2 —, —CHF—, —CF 2 —, —C ⁇ C—, —O—CH 2 —, —CH 2 —CH 2 —, —CF 2 —CF 2 —, —O—CH 2 —CH 2 —, —CH 2 —O—CH 2 —, —O—CH 2 —O—CH 2 —, —CF 2 —CH 2 —CF 2 —, —O—CF 2 —CH 2 —CF 2 —, —CH 2 —CH 2 —CH 2 —, —O—CH 2 —CH 2 —CH 2 —, —CF 2 —CF 2 —CF 2 —, —CH 2 —CH 2 —CH 2 —, —O—CH 2 —CH 2 —CH 2 —, —CF 2 —CF 2 —CF 2 —, —CH 2 —CH
  • the compound may be a compound represented by Formula 3 below:
  • the novel compound according to an embodiment may be used as an additive for a lithium secondary battery.
  • the compound may be included as an additive in at least one of a positive electrode, a negative electrode, and an electrolyte of a lithium secondary battery.
  • the compound when used as an additive for an electrolyte for a lithium secondary battery, it is possible to improve characteristics such as resistance during high-temperature storage, thermal stability, and low-temperature discharge capacity of a lithium secondary battery.
  • An electrolyte for a lithium secondary battery may include: a lithium salt; an organic solvent; and an additive, wherein the additive may include a cyclic sulfonyl group; and a silyl group linked thereto, the silyl group containing an unsaturated hydrocarbon group.
  • the electrolyte for a lithium secondary battery may improve characteristics such as resistance during high-temperature storage, thermal stability, and low-temperature discharge capacity of a lithium secondary battery, by including the above-described compound.
  • the electrolyte for a lithium secondary battery has an excellent effect of suppressing resistance at a high temperature of a lithium secondary battery containing a lithium transition metal oxide, which has a high nickel content, as a positive active material, and thus, a lithium secondary battery with improved lifespan and high temperature stability may be provided.
  • a lithium secondary battery having high output and high capacity may be manufactured by using a lithium transition metal oxide containing nickel and one or more other transition metals as a positive active material, and having a nickel content of, for example, 80 mol % or more, with respect to the total number of moles of the transition metal.
  • a lithium transition metal oxide having a high nickel content has an unstable surface structure, and therefore, gas generation is increased due to side reactions during charging and discharging of a battery and elution of transition metal such as nickel is aggravated.
  • a lithium secondary battery using a lithium transition metal oxide, which has a high nickel content, as a positive active material may have degraded lifespan characteristics and increased resistance at high temperatures, and thus, stability at high temperatures needs to be improved.
  • An electrolyte for a lithium secondary battery includes a compound having a cyclic sulfonyl group; and a silyl group linked thereto, the silyl group containing an unsaturated hydrocarbon group, and thus, a solid electrolyte interphase (SEI) film and/or a protective layer having low resistance may be formed, and accordingly, internal resistance of the battery may be reduced.
  • SEI solid electrolyte interphase
  • the compound having a cyclic sulfonyl group; and a silyl group linked thereto, the silyl group containing an unsaturated hydrocarbon group may be a compound represented by Formula 1 below:
  • a content of the compound may be in a range of about 0.001 wt % to about 20 wt %, with respect to the total weight of the electrolyte.
  • An upper limit of the content range of the compound may be 20 wt %, with respect to the total weight of the electrolyte, for example, 15 wt %, 10 wt %, 5 wt %, 3 wt %, or 1 wt %.
  • a lower limit of the content range of the compound may be 0.001 wt %, with respect to the total weight of the electrolyte, for example, 0.01 wt %, 0.05 wt %, 0.07 wt %, 0.1 wt %, 0.2 wt %, 0.3 wt %, 0.4 wt %, or 0.5 wt %.
  • a content range is not limited thereto, and may be adjusted within a commonly used range in consideration of combination with other additives, materials used as a positive active material, negative active material, etc.
  • the lithium salt may include at least one selected from the group consisting of LiPF 6 , LiBF 4 , LiSbF 6 , LiAsF 6 , LiClO 4 , LiCF 3 SO 3 , Li(CF 3 SO 2 ) 2 N, LiC 4 F 9 SO 3 , LiAlO 2 , LiAlCl 4 , LiN(C x F 2x+1 SO 2 )(C y F 2y+1 SO 2 ) (2 ⁇ x ⁇ 20, and 2 ⁇ y ⁇ 20), LiCl, LiI, lithium bis(fluorosulfonyl)imide (LiFSI), lithium bis(oxalato)borate (LiBOB), LiPO 2 F 2 , and compounds represented by Formulas 4 to 7 below, but is not limited thereto, and all that may be used as a lithium salt in the art may be used.
  • LiPF 6 LiBF 4 , LiSbF 6 , LiAsF 6 , LiClO 4 , LiCF 3 SO 3 , Li(
  • a concentration of the lithium salt in the electrolyte may be about 0.01 M to about 5.0 M, for example, about 0.05 M to about 5.0 M, for example, about 0.1 M to about 5.0 M, for example, about 0.1 M to about 2.0 M.
  • concentration of the lithium salt is within the above range, further improved lithium secondary battery characteristics may be obtained.
  • the organic solvent may be at least one selected from carbonate-based solvents, ester-based solvents, ether-based solvents, and ketone-based solvents.
  • EMC ethyl methyl carbonate
  • MPC methyl propyl carbonate
  • EPC ethyl propyl carbonate
  • DMC dimethyl carbonate
  • DEC diethyl carbonate
  • DPC dipropyl carbonate
  • PC propylene carbonate
  • EC ethylene carbonate
  • FEC fluoroethylene carbonate
  • VEC vinyl ethylene carbonate
  • BC butylene carbonate
  • ester-based solvent methyl propionate, ethyl propionate, propyl propionate, ethyl butyrate, methyl acetate, ethyl acetate, n-propyl acetate, dimethyl acetate, gamma butyrolactone, decanolide, gamma valerolactone, mevalonolactone, caprolactone, etc.
  • ether-based solvent dibutyl ether, tetraglyme, diglyme, dimethoxyethane, 2-methyltetrahydrofuran, tetrahydrofuran, etc.
  • a ketone-based solvent may be used; as a ketone-based solvent, cyclohexanone, etc. may be used; and as a nitrile-based solvent, acetonitrile (AN), succinonitrile (SN), adiponitrile, and the like may be used.
  • AN acetonitrile
  • SN succinonitrile
  • adiponitrile and the like may be used.
  • dimethyl sulfoxide, dimethylformamide, dimethylacetamide, tetrahydrofuran, etc. may be used, but the organic solvent is not necessarily limited thereto, and any solvent that may be used as an organic solvent in the art may be used.
  • the organic solvent may include a mixed solvent of about 50 vol % to about 95 vol % of chain carbonate and about 5 vol % to about 50 vol % of cyclic carbonate, for example, a mixed solvent of about 70 vol % to about 95 vol % of chain carbonate and about 5 vol % to about 30 vol % of cyclic carbonate.
  • the organic solvent may be a mixed solvent of three or more organic solvents.
  • the organic solvent may include at least one selected from the group consisting of ethyl methyl carbonate (EMC), methyl propyl carbonate (MPC), ethyl propyl carbonate (EPC), dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), propylene carbonate (PC), ethylene carbonate (EC), fluoroethylene carbonate (FEC), vinylene carbonate (VC), vinyl ethylene carbonate (VEC), butylene carbonate (BC), ethylpropionate, propylpropionate, ethylbutyrate, dimethylsulfoxide, dimethylformamide, dimethylacetamide, gamma-valerolactone, gamma-butyrolactone, and tetrahydrofuran, but is not limited thereto, and any that may be used as an organic solvent in the art may be used.
  • EMC ethyl methyl carbonate
  • DMC diethyl carbonate
  • the electrolyte may be in a liquid or gel state.
  • the electrolyte may be prepared by adding a lithium salt and the aforementioned additive to an organic solvent.
  • a lithium secondary battery includes a positive electrode including a positive active material; a negative electrode including a negative active material; and an electrolyte arranged between the positive electrode and the negative electrode, wherein at least one of the positive electrode, the negative electrode, and the electrolyte may include the above-described compound having a cyclic sulfonyl group; and a silyl group linked thereto, the silyl group containing an unsaturated hydrocarbon group.
  • at least an electrolyte of a lithium secondary battery may include the compound.
  • the lithium secondary battery may improve characteristics such as resistance during high-temperature storage, thermal stability, and low-temperature discharge capacity of a lithium secondary battery by including the above-described compound.
  • a positive active material includes a lithium transition metal oxide containing nickel and other transition metals.
  • an amount of nickel may be 60 mol % or more, for example, 75 mol % or more, for example, 80 mol % or more, for example, 85 mol % or more, or for example, 90 mol % or more, with respect to the total number of moles of the transition metal.
  • the lithium transition metal oxide may be a compound represented by Formula 8 below:
  • the lithium transition metal oxide may be at least one compound represented by Formulas 9 and 10 below:
  • the lithium transition metal oxide may be LiNi 0.6 Co 0.2 Mn 0.2 O 2 , LiNi 0.88 Co 0.08 Mn 0.04 O 2 , LiNi 0.8 CO 0.15 Mn 0.05 O 2 , LiNi 0.8 Co 0.1 Mn 0.1 O 2 , LiNi 0.88 Co 0.1 Mn 0.02 O 2 , LiNi 0.8 Co 0.15 Al 0.05 O 2 , LiNi 0.8 Co 0.1 Mn 0.2 O 2 , or LiNi 0.88 Co 0.1 Al 0.02 O 2 .
  • the positive active material includes at least one active material selected from the group consisting of Li—Ni—Co—Al (NCA), Li—Ni—Co—Mn (NCM), lithium cobalt oxide (LiCoO 2 ), lithium manganese oxide (LiMnO 2 ), lithium nickel oxide (LiNiO 2 ), and lithium iron phosphate (LiFePO 4 ).
  • active material selected from the group consisting of Li—Ni—Co—Al (NCA), Li—Ni—Co—Mn (NCM), lithium cobalt oxide (LiCoO 2 ), lithium manganese oxide (LiMnO 2 ), lithium nickel oxide (LiNiO 2 ), and lithium iron phosphate (LiFePO 4 ).
  • a negative active material may include at least one selected from a silicon-based compound, a carbon-based material, a composite of a silicon-based compound and a carbon-based compound, and silicon oxide (SiO x , 0 ⁇ x ⁇ 2).
  • the silicon-based compound may be silicon particles, silicon alloy particles, and the like.
  • a size of the silicon-based compound may be less than 200 nm, for example, about 10 nm to about 150 nm.
  • size may indicate an average particle diameter when the silicon-based compound is spherical, and may indicate an average long axis length when the silicon particles are non-spherical.
  • the carbon-based material may be crystalline carbon, amorphous carbon, or a mixture thereof.
  • the crystalline carbon may be graphite such as non-shaped, plate-like, flake-like, spherical, or fibrous natural graphite or artificial graphite, and the amorphous carbon may be soft carbon (low-temperature calcined carbon), or hard carbon, mesophase pitch carbide, calcined coke, and the like.
  • the composite of a silicon-based compound and a carbon-based compound may be a composite having a structure in which silicon nanoparticles are arranged on the carbon-based compound, a composite in which silicon particles are included on a surface of and inside the carbon-based compound, and a composite in which silicon particles are coated with the carbon-based compound and are included in the carbon-based compound.
  • the carbon-based compound may be graphite, graphene, graphene oxide, or a combination thereof.
  • the composite of a silicon-based compound and a carbon-based compound may be an active material obtained by dispersing silicon nanoparticles having an average particle diameter of about 200 nm or less on carbon-based compound particles and then coating with carbon, an active material in which silicon (Si) particles are present on and inside graphite, and the like.
  • An average particle diameter of secondary particles of the composite of a silicon-based compound and a carbon-based compound may be about 5 ⁇ m to about 20 ⁇ m.
  • An average particle diameter of the silicon nanoparticles may be 5 nm or more, for example, 10 nm or more, for example, 20 nm or more, for example, 50 nm or more, for example, 70 nm or more.
  • the average particle diameter of the silicon nanoparticles may be 200 nm or less, 150 nm or less, 100 nm or less, 50 nm or less, 20 nm or less, or 10 nm or less.
  • the average particle diameter of the silicon nanoparticles may be about 100 nm to about 150 nm.
  • An average particle diameter of secondary particles of the composite of a silicon-based compound and a carbon-based compound may be about 5 ⁇ m to about 20 ⁇ m, for example, 7 ⁇ m to about 15 ⁇ m, for example, 10 ⁇ m to about 13 ⁇ m.
  • a porous silicon composite cluster disclosed in Korean Patent Publication No. 10-2018-0031585, and a porous silicon composite cluster structure disclosed in Korean Patent Publication No. 10-2018-0056395 may be used.
  • Korean Patent Publication No. 10-2018-0031586 and Korean Patent Publication No. 10-2018-0056395 are incorporated herein by reference.
  • a silicon-carbon-based compound composite may be a porous silicon composite cluster containing a porous core including porous silicon composite secondary particles, and a shell including second graphene arranged on the core, wherein the porous silicon composite secondary particles include an aggregate of two or more silicon composite primary particles, and the silicon composite primary particles include: silicon; silicon oxide (SiO x ) (O ⁇ x ⁇ 2) arranged on the silicon; and first graphene arranged on the silicon oxide.
  • a silicon-carbon-based compound composite may be a porous silicon composite cluster, including porous silicon composite secondary particles, and second carbon flakes on at least one surface of the porous silicon composite secondary particles; and a porous silicon composite cluster structure, including a carbon-based coating film including amorphous carbon arranged on the porous silicon composite cluster, wherein the porous silicon composite secondary particles include an aggregate of two or more silicon composite primary particles, and the silicon composite primary particles include: silicon; silicon oxide (SiO x ) (O ⁇ x ⁇ 2) on at least one surface of the silicon; and first carbon flakes on at least one surface of the silicon oxide, and the silicon oxide exists in a form of a film, a matrix, or a combination thereof.
  • the first carbon flakes and the second carbon flakes may each exist in a form of a film, particle, matrix, or a combination thereof.
  • the first carbon flakes and the second carbon flakes may each be graphene, graphite, carbon fiber, graphene oxide, or the like.
  • the above-described composite of a silicon-based compound and a carbon-based compound may be a composite having a structure in which silicon nanoparticles are arranged on the carbon-based compound, a composite in which silicon particles are included on a surface of and inside the carbon-based compound, and a composite in which silicon particles are coated with the carbon-based compound and are included in the carbon-based compound.
  • the carbon-based compound may be graphite, graphene, graphene oxide, or a combination thereof.
  • the lithium secondary battery is not particularly limited in form, and may include a lithium ion battery, a lithium ion polymer battery, a lithium sulfur battery, and the like.
  • the lithium secondary battery may be prepared by the following method.
  • a positive electrode is prepared.
  • a positive electrode composition is prepared by mixing a positive active material, a conductive material, a binder, and a solvent.
  • the positive active material composition may be directly coated on a metal current collector to prepare a positive electrode plate.
  • the positive active material composition may be cast on a separate support and then a film separated from the support may be laminated on a metal current collector to prepare a positive electrode plate.
  • the positive electrode is not limited to the forms listed above and may have forms other than the above forms.
  • the positive active material may be, for example, a metal oxide containing lithium, and any one commonly used in the art may be used without limitation.
  • a complex oxide of lithium and a metal selected from cobalt, manganese, nickel, and combinations thereof may be used, for specific examples, any compound represented by any one of the following formulas may be used: Li a A 1-b B 1 b D 1 2 (wherein 0.90 ⁇ a ⁇ 1.8, and 0 ⁇ b ⁇ 0.5); Li a E 1-b B 1 b O 2-c D 1 c , (wherein 0.90 ⁇ a ⁇ 1.8, 0 ⁇ b ⁇ 0.5, and 0 ⁇ c ⁇ 0.05); Li a E 1-b B 1 b O 2-c D 1 c (wherein 0 ⁇ b ⁇ 0.5, and 0 ⁇ c ⁇ 0.05); Li a Ni 1-b-c Co b B 1 c D 1 ⁇ (wherein 0.90 ⁇ a ⁇ 1.8, 0 ⁇ b ⁇ 0.5, 0 ⁇ c ⁇ 0.05, and 0 ⁇ 2); Li a Ni 1-b-c Co
  • A may be Ni, Co, Mn, or a combination thereof
  • B 1 may be Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, a rare earth element, or a combination thereof
  • D 1 may be O, F, S, P, or a combination thereof
  • E may be Co, Mn, or a combination thereof
  • F 1 may be F, S, P, or a combination thereof
  • G may be Al, Cr, Mn, Fe, Mg, La, Ce, Sr, V, or a combination thereof
  • Q may be Ti, Mo, Mn, or a combination thereof
  • I may be Cr, V, Fe, Sc, Y, or a combination thereof
  • J may be V, Cr, Mn, Co, Ni, Cu, or a combination thereof.
  • a compound with a coating layer on a surface of the above-mentioned compound may be used, or a mixture of the above-mentioned compound and the compound with a coating layer may be used.
  • the coating layer may include a compound of a coating element, such as an oxide of a coating element, a hydroxide of a coating element, an oxyhydroxide of a coating element, an oxycarbonate of a coating element, or a hydroxycarbonate of a coating element.
  • Compounds constituting the coating layer may be amorphous or crystalline.
  • the coating element included in the coating layer Mg, Al, Co, K, Na, Ca, Si, Ti, V, Sn, Ge, Ga, B, As, Zr, or mixtures thereof may be used.
  • any coating method for example, spray coating, an immersion method, etc.
  • any coating method may be used as long as the compound may be coated in a way that does not adversely affect physical properties of the positive active material by using these elements, and since this may be well understood by those skilled in the art, a detailed description thereof will be omitted.
  • Carbon black, graphite fine particles, etc. may be used as the conductive material, but the conductive material is not limited thereto, and any material that may be used as a conductive material in the art may be used.
  • binder examples include vinylidene fluoride/hexafluoropropylene copolymer, polyvinylidene fluoride (PVDF), polyacrylonitrile, polymethylmethacrylate, polytetrafluoroethylene (PTFE), mixtures thereof, or styrene butadiene rubber-based polymer or the like, but it is not necessarily limited thereto, and any binder used in the art may be used.
  • PVDF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • N-methylpyrrolidone, acetone, or water may be used as the solvent, but the solvent is not limited thereto, and any solvent that may be used in the art may be used.
  • Amounts of the positive active material, conductive material, binder, and solvent are levels commonly used in lithium batteries. Depending on an intended use and configuration of the lithium battery, one or more of the conductive material, binder, and solvent may be omitted.
  • a negative active material composition is prepared by mixing a negative active material, a conductive material, a binder, and a solvent.
  • the negative active material composition may be directly coated on a metal current collector to prepare a negative electrode plate.
  • the negative active material composition may be cast on a separate support and then a film separated from the support may be laminated on a metal current collector to prepare a negative electrode plate.
  • the negative active material any that may be used as a negative active material in the related art may be used.
  • the negative active material may include one or more selected from lithium metals, metals alloyable with lithium, transition metal oxides, non-transition metal oxides, and carbon-based materials.
  • the metals alloyable with lithium may be Si, Sn, Al, Ge, Pb, Bi, Sb, and Si—Y alloy (Y may be an alkali metal, alkaline earth metal, group 13 element, group 14 element, transition metal, rare earth element, or a combination thereof, and is not Si), Sn—Y alloy (Y may be an alkali metal, alkaline earth metal, group 13 element, group 14 element, transition metal, rare earth element, or a combination thereof, and is not Sn), and the like.
  • the element Y may be, for example, Mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, Hf, Rf, V, Nb, Ta, db, Cr, Mo, W, Sg, Tc, Re, Bh, Fe, Pb, Ru, Os, Hs, Rh, Ir, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al, Ga, Sn, In, TI, Ge, P, As, Sb, Bi, S, Se, Te, Po, or a combination thereof.
  • the transition metal oxide may be lithium titanium oxide, vanadium oxide, or lithium vanadium oxide.
  • the non-transition metal oxide may be SnO 2 , SiO x (0 ⁇ x ⁇ 2), etc.
  • the carbon-based material may be crystalline carbon, amorphous carbon, or a mixture thereof.
  • the crystalline carbon may be graphite such as amorphous, plate-like, flake-like, spherical, or fibrous natural graphite or artificial graphite, and the amorphous carbon may be soft carbon (low-temperature calcined carbon), or hard carbon, mesophase pitch carbide, calcined coke, and the like.
  • the same conductive material and binder as in the case of the positive active material composition may be used.
  • Amounts of the negative active material, conductive material, binder, and solvent are levels commonly used in lithium batteries. Depending on an intended use and configuration of the lithium battery, one or more of the conductive material, binder, and solvent may be omitted.
  • one or more of the conductive material, binder, and solvent may be omitted.
  • a separator having low resistance to ionic movement of an electrolytic solution and excellent impregnation ability for an electrolytic solution may be used.
  • the separator may be, for example, selected from glass fiber, polyester, Teflon, polyethylene, polypropylene, polytetrafluoroethylene (PTFE), or combinations thereof, and may be in a form of a nonwoven or woven fabric.
  • a winding separator such as polyethylene, polypropylene, and the like may be used in a lithium ion cell, and a separator having an excellent impregnation ability for an organic lelectrolytic solution may be used in a lithium ion polymer cell.
  • the separator may be prepared according to the following method.
  • a separator composition is prepared by mixing a polymer resin, a filler, and a solvent.
  • the separator composition may be directly coated on an electrode and dried to form a separator.
  • a separator film peeled from the support may be stacked on an electrode to form a separator.
  • the polymer resin used for manufacturing the separator is not particularly limited, and any substance used in a binder of a electrode plate may be used.
  • any substance used in a binder of a electrode plate may be used.
  • vinylidene fluoride/hexafluoropropylene copolymer, polyvinylidene fluoride (PVDF), polyacrylonitrile, polymethyl methacrylate, or a mixture thereof may be used.
  • the separator includes, but is not limited to, for example, polyethylene separator (PES), polypropylene separator (PPS), ceramic coated separator (CCS), polymer coated separator (PCS), multi-layer coated separator (MCS), multi-functional separator (MFS), etc., and a combination thereof is also possible.
  • PES polyethylene separator
  • PPS polypropylene separator
  • CCS ceramic coated separator
  • PCS polymer coated separator
  • MCS multi-layer coated separator
  • MFS multi-functional separator
  • the lithium battery 1 includes a positive electrode 3 , a negative electrode 2 , and a separator 4 .
  • the above-described positive electrode 3 , negative electrode 2 , and separator 4 are wound or folded to be accommodated in the battery case 5 .
  • an organic liquid electrolyte is injected into the battery case 5 and sealed with a cap assembly 6 to complete a lithium battery 1 .
  • the battery case may be a cylindrical shape, a prismatic shape, or a thin film type.
  • the lithium battery may be a large-sized thin film battery.
  • the lithium battery may be a lithium ion battery.
  • an electrode assembly having a cylindrical shape, in which a separator is wound between a positive electrode and a negative electrode may be formed, inserted into a cylindrical can, and then an electrolytic solution may be injected into the cylindrical can.
  • the cylindrical can may be formed of steel, steel alloy, nickel-plated steel, nickel-plated steel alloy, aluminum, aluminum alloy, or an equivalent material thereof, but the material is not limited thereto.
  • a beading part recessed inwardly may be formed around a cap assembly at the bottom of the cap assembly to prevent the cap assembly from escaping to the outside, and a crimping part bent inward may be formed on the beading part.
  • a plurality of the battery structure in which a separator is arranged between a positive electrode and a negative electrode, may be stacked to form a battery pack, and such a battery pack may be used in all devices requiring high capacity and high output.
  • the battery pack may be used in laptops, smartphones, electric vehicles, and the like.
  • a lithium secondary battery according to an embodiment has a significantly reduced direct current internal resistance (DC-IR) increase rate compared to a lithium secondary battery employing a general nickel-rich lithium nickel composite oxide as a positive active material, thereby exhibiting excellent battery characteristics.
  • DC-IR direct current internal resistance
  • An operating voltage of the lithium secondary battery to which the positive electrode, the negative electrode, and the electrolyte are applied may have, for example, a lower limit of about 2.5 V to about 2.8 V and an upper limit of about 4.1 V or more, for example, about 4.1 V to about 4.47 V.
  • the lithium secondary battery may be applied to, for example, a power tool that moves by receiving motivity from a motor run by a battery; electric vehicles (EVs) including hybrid electric vehicles (HEVs), plug-in hybrid electric vehicles (PHEVs), and the like; electric two-wheeled vehicles including E-bikes and E-scooters; electric golf carts; power storage systems, and the like, but is not limited thereto.
  • EVs electric vehicles
  • HEVs hybrid electric vehicles
  • PHEVs plug-in hybrid electric vehicles
  • electric two-wheeled vehicles including E-bikes and E-scooters
  • electric golf carts power storage systems, and the like, but is not limited thereto.
  • alkyl group means a branched or unbranched aliphatic hydrocarbon group.
  • an alkyl group may be substituted or unsubstituted.
  • the alkyl group includes a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, etc., but not limited thereto, and each of these may be optionally substituted in another embodiment.
  • an alkyl group may contain 1 to 6 carbon atoms.
  • a C 1 -C 6 alkyl group may include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a pentyl group, a 3-pentyl group, a hexyl group, and the like, but is not limited thereto.
  • One or more hydrogen atoms in the alkyl group may be substituted with a halogen atom, a C 1 -C 20 alkyl group substituted with a halogen atom (for example, CF 3 , CHF 2 , CH 2 F, CCl 3 , etc.), a C 1 -C 20 alkoxy group, a C 2 -C 29 alkoxyalkyl group, a hydroxyl group, a nitro group, a cyano group, an amino group, an amidino group, hydrazine, hydrazone, a carboxyl group or a salt thereof, a sulfonyl group, a sulfamoyl group, a sulfonic acid group or a salt thereof, phosphoric acid or a salt thereof, or a C 1 -C 20 alkyl group, a C 2 -C 20 alkenyl group, a C 2 -C 20 alkynyl group, a C 1 -
  • alkenyl group refers to a hydrocarbon group including at least one carbon-carbon double bond, and having a carbon number of 2 to 20, and includes an ethenyl group, 1-propenyl group, a 2-propenyl group, a 2-methyl-1-propenyl group, 1-butenyl group, 2-butenyl group, cyclopropenyl group, cyclopentenyl, cyclohexenyl, and the like, but is not limited thereto.
  • the alkenyl group may be substituted or unsubstituted.
  • the alkenyl group may have a carbon number of 2 to 40.
  • alkynyl group refers to a hydrocarbon group including at least one carbon-carbon triple bond, and having a carbon number of 2 to 20, and includes an ethynyl group, 1-propynyl group, 1-butynyl group, 2-butynyl group, etc., but is not limited thereto.
  • the alkynyl group may be substituted or unsubstituted.
  • the alkynyl group may have a carbon number of 2 to 40.
  • a substituent is derived from an unsubstituted parent group, in which one or more hydrogen atoms are replaced by another atom or functional group.
  • a functional group when a functional group is considered to be “substituted”, it means that the functional group is substituted with one or more substituents independently selected from the group consisting of C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 1 -C 20 alkoxy, halogen, a cyano group, a hydroxy group, and a nitro group.
  • the functional group may be substituted with the substituents described above.
  • halogen includes fluorine, bromine, chlorine, iodine, and the like.
  • Alkoxy refers to “alkyl-O—”, wherein alkyl is as described above.
  • alkoxy group include a methoxy group, an ethoxy group, a 2-propoxy group, a butoxy group, a t-butoxy group, a pentyloxy group, and a hexyloxy group.
  • One or more hydrogen atoms of the alkoxy group may be substituted with the same substituents as in the case of the above-mentioned alkyl group.
  • Heteroaryl means a monocyclic or bicyclic organic group including at least one heteroatom selected from N, O, P, or S, and carbon as the remaining ring atom.
  • the heteroaryl group may include, for example, 1 to 5 heteroatoms, and 5 to 10 ring members. S or N may be oxidized to have various oxidation states.
  • heteroaryl examples include thienyl, furyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, 1,2,3-oxadiazolyl, 1,2,4-oxadiazolyl, 1,2,5-oxadiazolyl, 1,3,4-oxadiazolyl, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,2,5-thiadiazolyl, 1,3,4-thiadiazolyl, isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-yl, oxazol-2-yl, oxazol-4-yl, oxazol-5-yl, isoxazol-3-yl, isoxazol-4-yl, isoxazol-5-yl, 1,2,4-triazol-3-yl, 1,2,4-triazole-5-yl, 1,2,3-triazol-4-yl
  • heteroaryl includes cases in which a heteroaromatic ring is optionally fused to at least one aryl, cycloaliphatic, or heterocycle.
  • carrier refers to a saturated or partially unsaturated, non-aromatic monocyclic, bicyclic, or tricyclic hydrocarbon group.
  • Examples of the monocyclic hydrocarbon include cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, and the like.
  • bicyclic hydrocarbon examples include bornyl, decahydronaphthyl, bicyclo[2.1.1]hexyl, bicyclo[2.1.1]heptyl, bicyclo[2.2.1]heptenyl, or bicyclo[2.2.2]octyl.
  • tricyclic hydrocarbon examples include adamantyl, and the like.
  • One or more hydrogen atoms of the carbocycle may be substituted with the same substituents as in the case of the above-mentioned alkyl group.
  • the final Compound 2 was prepared through the following synthesis process:
  • 97 wt % of LCO as a positive active material 0.5 wt % of artificial graphite power as conductive materials and 0.8 wt % of carbon black as conductive materials, and 1.7 wt % of polyvinylidene fluoride (PVDF) were put into N-methyl-2-pyrrolidone, and was stirred for 4 hours by using a mechanical stirrer to prepare positive active material slurry.
  • the slurry was uniformly applied on a 12 ⁇ m thick aluminum current collector by using a coater and dried with hot air at 100° C. Then the dried product was roll-pressed to prepare a positive electrode.
  • negative active material As a negative active material, 98 wt % of artificial graphite, 1 wt % of styrene-butadiene rubber (SBR), and 1 wt % of carboxymethyl cellulose (CMC) were mixed and dispersed in water to prepare negative active material slurry.
  • the slurry was uniformly applied on a 10 ⁇ m thick copper current collector in a continuous manner by using a coater, and dried with hot air at 100° C. Then the dried product was roll-pressed to prepare a negative electrode.
  • a coin cell was prepared by using the prepared positive and negative electrodes, a 14 ⁇ m thick polyethylene separator, and the electrolyte.
  • a lithium secondary battery was prepared in the same manner as in Example 1, except that 0.5 wt % of Compound 2 synthesized in Preparation Example 1 was added.
  • a coin cell was prepared in the same manner as in Example 1, except that 1.0 wt % of Compound 2 synthesized in Preparation Example 1 was added.
  • a coin cell was prepared in the same manner as in Example 1, except that an electrolyte, into which Compound 2 synthesized in Preparation Example 1 was not added, was used.
  • Coin cells prepared in Examples 1 to 3 and Comparative Example 1 were charged to a state of charge (SOC) of 100% (fully charged, when a battery is charged/discharged at 3.0 V to 4.47 V, and when total charge capacity of the battery is set to 100%, the battery is charged to have charge capacity of 100%), under conditions of constant current charging at 0.2 C until the voltage reaches 4.47 V-constant voltage charging, and cut-off at 0.02 C, and then the batteries were stored at 60° C. for 10 days.
  • SOC state of charge
  • the coin cells of Examples 1 to 3 have decreased AC-IR values, and a reduced AC-IR increase rate during high-temperature storage at 60° C., by including Compound 2 synthesized in Preparation Example 1 in the electrolyte, compared to the case not including Compound 2.
  • the initial resistance and AC-IR increase rate were the lowest when 0.5 wt % of Compound 2 was contained.
  • Evaluation Example 2 Evaluation of Resistance During Storage at High Temperature (60° C.) by Using EIS
  • the coin cells manufactured in Examples 1 to 3 and Comparative Example 1 were stored at a high temperature of 60° C. for 10 days in the same manner as in Evaluation Example 1, and internal resistance was measured by using electrochemical impedance spectroscopy (EIS), before storage (Day 0), 4 days after storage (Day 0), and 10 days after storage(Day 10). The results are respectively shown in FIGS. 3 to 5 .
  • EIS electrochemical impedance spectroscopy
  • the coin cells of Examples 2 and 3 showed a smaller decrease of low-temperature discharge capacity compared to the coin cell of Comparative Example 1, indicating that discharge characteristics at a low temperature were improved.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Secondary Cells (AREA)
US18/013,841 2021-03-16 2022-02-28 Novel compound, and additive, electrolyte and lithium secondary battery which comprise same Pending US20230402651A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
KR1020210034237A KR20220129390A (ko) 2021-03-16 2021-03-16 신규 화합물, 이를 포함하는 첨가제, 전해질 및 리튬 이차전지
KR10-2021-0034237 2021-03-16
PCT/KR2022/002844 WO2022196972A1 (ko) 2021-03-16 2022-02-28 신규 화합물, 이를 포함하는 첨가제, 전해질 및 리튬 이차전지

Publications (1)

Publication Number Publication Date
US20230402651A1 true US20230402651A1 (en) 2023-12-14

Family

ID=83320718

Family Applications (1)

Application Number Title Priority Date Filing Date
US18/013,841 Pending US20230402651A1 (en) 2021-03-16 2022-02-28 Novel compound, and additive, electrolyte and lithium secondary battery which comprise same

Country Status (5)

Country Link
US (1) US20230402651A1 (zh)
EP (1) EP4310092A1 (zh)
KR (1) KR20220129390A (zh)
CN (1) CN117062823A (zh)
WO (1) WO2022196972A1 (zh)

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5399556B2 (ja) * 2010-04-26 2014-01-29 三井化学株式会社 環状スルホン化合物を含有する非水電解液、及びリチウム二次電池
JP5832315B2 (ja) * 2012-01-20 2015-12-16 住友精化株式会社 電解液用溶媒、および電気化学デバイス用電解液
KR101437073B1 (ko) * 2012-06-08 2014-09-02 주식회사 엘지화학 리튬 이차전지용 비수 전해액 및 이를 구비한 리튬 이차전지
JP2016197508A (ja) * 2015-04-02 2016-11-24 旭化成株式会社 非水電解液添加剤、非水電解液、リチウムイオン二次電池
KR101932959B1 (ko) 2016-09-19 2019-03-15 김재복 2차 사고 예방을 위한 차량용 긴급 알림 장치 및 그 방법
KR102357975B1 (ko) 2016-09-19 2022-02-04 삼성전자주식회사 다공성 실리콘 복합체 클러스터, 그 탄소 복합체, 이를 포함한 전극, 리튬 전지, 전계 방출 소자, 바이오센서, 반도체 소자 및 열전소자
KR102409817B1 (ko) 2016-11-18 2022-06-17 삼성에스디아이 주식회사 다공성 실리콘 복합체 클러스터 구조체, 이를 포함한 탄소 복합체, 그 제조방법, 이를 포함한 전극, 및 리튬 전지, 소자
KR20190055733A (ko) * 2017-11-15 2019-05-23 삼성전자주식회사 리튬전지 전해질 첨가제, 이를 포함하는 유기전해액 및 리튬전지

Also Published As

Publication number Publication date
EP4310092A1 (en) 2024-01-24
KR20220129390A (ko) 2022-09-23
WO2022196972A1 (ko) 2022-09-22
CN117062823A (zh) 2023-11-14

Similar Documents

Publication Publication Date Title
US20220263131A1 (en) Electrolyte additive for lithium secondary battery, electrolyte for lithium secondary battery including the same, and lithium secondary battery
US20190148772A1 (en) Electrolyte additive for lithium battery, organic electrolyte solution including the same, and lithium battery including the same
US11527773B2 (en) Lithium battery
EP3506411B1 (en) Organic electrolyte solution and lithium battery including the same
US20120045697A1 (en) Electrolyte for rechargeable lithium battery, and rechargeable lithium battery including same
US20200251780A1 (en) Electrolyte, lithium battery including the same, and method of manufacturing the lithium battery
EP3696901A1 (en) Lithium secondary battery
US20230327200A1 (en) Electrolyte for lithium secondary battery, and lithium secondary battery comprising same
US20220263132A1 (en) Electrolyte additive for lithium secondary battery, electrolyte for lithium secondary battery including the same, and lithium secondary battery including electrolyte
US20230402651A1 (en) Novel compound, and additive, electrolyte and lithium secondary battery which comprise same
EP4283736A1 (en) Electrolyte for lithium secondary battery and lithium secondary battery comprising same
US20230344002A1 (en) Electrolyte for lithium secondary battery, and lithium secondary battery comprising same
US20240186577A1 (en) Electrolyte for lithium secondary battery, and lithium secondary battery including the same
US20240088439A1 (en) Electrolyte for lithium secondary battery and lithium secondary battery including electrolyte
US20230268509A1 (en) Cathode for lithium secondary battery and lithium secondary battery comprising same
US20240120539A1 (en) Electrolyte composition for lithium secondary battery and lithium secondary battery including the same
US20240186578A1 (en) Electrolyte for lithium secondary battery and lithium secondary battery including the same
US20220407113A1 (en) Organic electrolytic solution and lithium battery including the same
KR20230036357A (ko) 리튬 이차전지용 전해질 및 이를 포함하는 리튬 이차전지
KR20170050685A (ko) 리튬전지
KR20240070295A (ko) 리튬이차전지용 전해질 및 이를 포함하는 리튬이차전지
KR20240071838A (ko) 리튬이차전지용 전해질 및 이를 포함하는 리튬이차전지

Legal Events

Date Code Title Description
STPP Information on status: patent application and granting procedure in general

Free format text: DOCKETED NEW CASE - READY FOR EXAMINATION